In situ beam reduction of Pu(IV) and Bk(IV) as a route to trivalent transuranic coordination complexes with hydroxypyridinone chelators

Korey P Carter; Jennifer N Wacker; Kurt F Smith; Gauthier J P Deblonde; Liane M Moreau; Julian A Rees; Corwin H Booth; Rebecca J Abergel

doi:10.1107/S1600577522000200

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In situ beam reduction of Pu(IV) and Bk(IV) as a route to trivalent transuranic coordination complexes with hydroxypyridinone chelators

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In situ beam reduction of Pu(IV) and Bk(IV) as a route to trivalent transuranic coordination complexes with hydroxypyridinone chelators

Korey P Carter, Jennifer N Wacker, Kurt F Smith, Gauthier J P Deblonde, Liane M Moreau, Julian A Rees, Corwin H Booth and Rebecca J Abergel

Journal of synchrotron radiation, Vol.29(Pt 2), pp.315-322

03/01/2022

DOI: 10.1107/S1600577522000200

PMCID: PMC8900832

PMID: 35254293

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Abstract

The solution-state interactions of plutonium and berkelium with the octadentate chelator 3,4,3-LI(1,2-HOPO) (343-HOPO) were investigated and characterized by X-ray absorption spectroscopy, which revealed in situ reductive decomposition of the tetravalent species of both actinide metals to yield Pu(III) and Bk(III) coordination complexes. X-ray absorption near-edge structure (XANES) measurements were the first indication of in situ synchrotron redox chemistry as the Pu threshold and white-line position energies for Pu-343-HOPO were in good agreement with known diagnostic Pu(III) species, whereas Bk-343-HOPO results were found to mirror the XANES behavior of Bk(III)-DTPA. Extended X-ray absorption fine structure results revealed An-O bond distances of 2.498 (5) and 2.415 (2) Å for Pu and Bk, respectively, which match well with bond distances obtained for trivalent actinides and 343-HOPO via density functional theory calculations. Pu(III)- and Bk(III)-343-HOPO data also provide initial insight into actinide periodicity as they can be compared with previous results with Am(III)-, Cm(III)-, Cf(III)-, and Es(III)-343-HOPO, which indicate there is likely an increase in 5f covalency and heterogeneity across the actinide series.

Berkelium

Chelating Agents - chemistry

Coordination Complexes

Plutonium - chemistry

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Title: Subtitle: In situ beam reduction of Pu(IV) and Bk(IV) as a route to trivalent transuranic coordination complexes with hydroxypyridinone chelators
Creators: Korey P Carter - University of Iowa, Chemistry
Jennifer N Wacker - Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA 94720, USA
Kurt F Smith - Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA 94720, USA
Gauthier J P Deblonde - Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA 94720, USA
Liane M Moreau - Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA 94720, USA
Julian A Rees - Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA 94720, USA
Corwin H Booth - Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA 94720, USA
Rebecca J Abergel - Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA 94720, USA
Resource Type: Journal article
Publication Details: Journal of synchrotron radiation, Vol.29(Pt 2), pp.315-322
DOI: 10.1107/S1600577522000200
PMID: 35254293
PMCID: PMC8900832
NLM abbreviation: J Synchrotron Radiat
ISSN: 1600-5775
eISSN: 1600-5775
Grant note: DE-AC02-05CH11231 / US Department of Energy, Office of Science DE-AC02-76SF00515 / US Department of Energy, Office of Science
Language: English
Date published: 03/01/2022
Academic Unit: Chemistry
Record Identifier: 9984277547002771

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